Chloroauric acid

Chloroauric acid
Names
Other names
Hydrogen tetrachloroaurate,
Chlorauric acid,
Aurochloric acid,
Aurate(1-), tetrachloro-, hydrogen, (SP-4-1)-,
Hydrogen aurichloride
Identifiers
16903-35-8 Yes
16961-25-4 (trihydrate) 
ChemSpider 26171 Yes
Jmol-3D images Image
PubChem 28133
Properties
HAuCl4
Molar mass 339.785 g/mol (anhydrous)
393.833 g/mol (trihydrate)
411.85 g/mol (tetrahydrate)
Appearance orange-yellow needle-like crystals
hygroscopic
Density 3.9 g/cm3 (anhydrous)
2.89 g/cm3 (tetrahydrate)
Melting point 254 °C (489 °F; 527 K) (decomposes)
350 g HAuCl4 / 100 g H2O
Solubility soluble in alcohol, ester, ether, ketone
Structure
Crystal structure monoclinic
Hazards
MSDS JT Baker
EU classification not listed
NFPA 704
Flammability code 0: Will not burn. E.g., water Health code 3: Short exposure could cause serious temporary or residual injury. E.g., chlorine gas Reactivity code 1: Normally stable, but can become unstable at elevated temperatures and pressures. E.g., calcium Special hazards (white): no codeNFPA 704 four-colored diamond
0
3
1
Related compounds
Other anions
 Tetrabromoauric acid
Except where noted otherwise, data is given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
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Infobox references

Chloroauric acid is an inorganic compound with the chemical formula HAuCl
4. Both the trihydrate and tetrahydrate are known. It is an orange-yellow solid, a common precursor to other gold compounds and an intermediate in the purification of gold metal. Both the trihydrate and tetrahydrate are available commercially.

Chemical properties

Acidity

A hydrogen center in the oxidaniumyl group (-OH+
2) in oxidanium cations such as oxonium can separate from the molecule by heterolysis:

H
3O+
 → H
2O + H+

Because of this release of the proton (H+
), chloroauric acid has an acidic character. Chloroauric acid is a strong monoprotic conjugate acid. Although chloroauric acid forms aqueous solutions, such solutions are unstable due to hydrolysis of the tetrachloridoaurate ion. An aqueous solution consists of an ensemble of anions in equilibrium, with the overall reaction being:

H
3OAuCl
4 + 2 H
2O is in a disfavored equilibrium with Au(OH)
3 + 4 HCl

Thus, unless outgassing hydrogen chloride is replenished, aqueous chloroauric acid will decompose to auric hydroxide. However, this decomposition route is unlikely, as HCl is a strong acid, and thus it is very unlikely that Cl− ions will combine with H+ to form HCl in an aqueous solution.

Structure

The crystalline tetrahydrate is known to contain H5O2+ AuCl4− and two water molecules.[1] The AuCl4− anion has square planar molecular geometry. The Au-Cl distances are around 2.28 Å. Other d8 complexes adopt similar structures, e.g. [PtCl4]2−.

Solute properties

Solid chloroauric acid is a hydrophilic (ionic) protic solute. It is soluble not only in water, but also in many oxygen-containing solvents, such as alcohols, esters, ethers, and ketones. For example, in dry dibutyl ether of diethylene glycol, the solubility exceeds 1 mol/L. Saturated solutions in the organic solvents often are the liquid solvates of specific stoichiometry.

When heated in air of solid HAuCl4•n H2O, it melts in the water of crystallization, quickly darkens and becomes dark brown.

Chemical reactions

Upon treating chloroauric acid with a standard base, it converts to metal tetrachloridoaurate and water. The related thallium (sic?) salt is poorly soluble in all nonreacting solvents. Salts of quaternary ammonium cations are known.[2] Other complex salts include [Au(bipy)Cl2][AuCl4][3] and [Co(NH3)6][AuCl4]Cl2.

Partial reduction of chloroauric acid gives oxonium dichloridoaurate(1−).[4] Reduction may also yield other gold(I) complexes, especially with organic ligands. Often the ligand serves as reducing agent as illustrated with thiourea ((H2N)2CS):

AuCl4− + 4 (H2N)2CS + H2O → Au[(H2N)2CS]2+ + (H2N)2CO + S + 2 Cl− + 2 HCl

Chloroauric acid is the precursor to gold nanoparticles by precipitation onto mineral supports.[5] <--- (Wrong reference?) Heating of HAuCl4•n H2O in a stream of chlorine gives gold(III) chloride (Au2Cl6).[6]

Production

It is produced by dissolving gold in aqua regia (a mixture of concentrated nitric and hydrochloric acids) followed by careful evaporation of the solution:[7]

Au + HNO3 + 4 HCl → HAuCl4 + NO + 2 H2O

Under some conditions, oxygen can be used as the oxidant.[8] For higher efficiency, these processes are conducted in autoclaves, which allows greater control of temperature and pressure. Alternatively, a solution of HAuCl4 can be produced by electrolysis of gold metal in hydrochloric acid:

2 Au + 8 HCl → 2 HAuCl4 + 3 H2

To prevent the deposition of gold on the cathode, the electrolysis is carried out in a cell equipped with a membrane. This method is used for refining gold. Some gold remains in solution in the form of [AuCl2]−.[9]

A solution of HAuCl4 can also be obtained by the action of chlorine or chlorine water on metallic gold in hydrochloric acid:

2 Au + 3 Cl2 + 2 HCl → 2 HAuCl4

This reaction is widely used for extracting gold from electronic and other "rich" materials.

In addition to the above routes, many other ways exist to dissolve gold, differing in the choice of the oxidant (hydrogen peroxide, hypochlorites) or variations of conditions. It is possible also to convert the trichloride (Au2Cl6) or the oxide (Au2O3•x H2O).

Uses

Chloroauric acid is the precursor used in the purification of gold by electrolysis.

Liquid-liquid extraction of chloroauric acid is used for the recovery, concentrating, purification, and analytical determinations of gold. Of great importance is the extraction of HAuCl4 from hydrochloric medium by oxygen-containing extractants, such as alcohols, ketones, ethers and esters. The concentration of gold(III) in the extracts may exceed 1 mol/L.[10][11][12] The most frequently used extractants for this purpose are dibutyl glycol, methyl isobutyl ketone, tributyl phosphate, dichlorodiethyl ether (chlorex).

Health effects and safety

Chloroauric acid is a strong eye, skin, and mucous membrane irritant. Prolonged skin contact with chloroauric acid may result in tissue destruction. Concentrated chloroauric acid is corrosive to skin and must, therefore, be handled with appropriate care, since it can cause skin burn, permanent eye damage, and irritation to the mucous membrane. Gloves are worn when handling the compound.

References

  1. ↑ Williams, Jack Marvin; Peterson, Selmer Wiefred (1969). "Example of the [H5O2]+ion. Neutron diffraction study of tetrachloroauric acid tetrahydrate". Journal of the American Chemical Society 91 (3): 776–777. doi:10.1021/ja01031a062. ISSN 0002-7863.
  2. ↑ Makotchenko, E. V.; Kokovkin, V. V. (2010). "Solid contact [AuCl4]−-selective electrode and its application for evaluation of gold(III) in solutions". Russian Journal of General Chemistry 80 (9): 1733. doi:10.1134/S1070363210090021.
  3. ↑ Mironov, I. V.; Tsvelodub, L. D. "Equilibria of the substitution of pyridine, 2,2 '-bipyridyl, and 1,10-phenanthroline for Cl− in AuCl4− in aqueous solution" Russian Journal of Inorganic Chemistry. 2001, vol. 46, p. 143–148.
  4. ↑ Huang, Xiaohua; Peng, Xianghong; Wang, Yiqing; Yuxiang, Wang; Shin, Dong M.; El-Sayed, Mostafa A.; Nie, Shuming (26 October 2010). "A reexamination of active and passive tumor targeting by using rod-shaped gold nanocrystals and covalently conjugated peptide ligands". ACS Nano (ACS Publications) 4 (10): 5887–5896. doi:10.1021/nn102055s.
  5. ↑ Gunanathan, C.; Ben-David, Y.; Milstein, D. (2007). "Direct Synthesis of Amides from Alcohols and Amines with Liberation of H2". Science 317 (5839): 790–792. doi:10.1126/science.1145295. PMID 17690291.
  6. ↑ Mellor J. W. A comprehensive treatise on inorganic and theoretical chemistry. Vol. 3. 1946. p. 593.
  7. ↑ Handbook of Preparative Inorganic Chemistry, 2nd Ed. Edited by G. Brauer, Academic Press, 1963, New York.
  8. ↑ Novoselov, R. I.; Makotchenko, E. V. "Application of oxygen as ecologically pure reagent for the oxidizing of non-ferrous and precious metals, sulphide minerals" Chemistry for sustainable development, 1999, vol. 7, p. 321–330.
  9. ↑ Belevantsev V. I., Peschevitskii, B. I.; Zemskov, S. V. "New data on chemistry of gold compounds in solutions" Izvestiya Sibirskogo Otdeleniya AN SSSR, ser. khim. nauk. 1976. N4. Issue 2. P. 24–45.
  10. ↑ Mironov, I. V.; Natorkhina, K. I. (2012). "On the selection of extractant for the preparation of high-purity gold". Russian Journal of Inorganic Chemistry 57 (4): 610. doi:10.1134/S0036023612040195.
  11. ↑ Feather, A; KC Sole; Lj Bryson (July 1997). "Gold refining by solvent extraction—the minataur™ process" (PDF). Journal of the Southern African Institute of Mining and Metallurgy: 169–173. Retrieved 2013-03-17.
  12. ↑ Morris D. F. C., Khan M. A. "Application of solvent extraction to the refining of precious metals, Part 3: purification of gold" Talanta, 1968. vol. 15, pp. 1301—1305.